WO2018093230A2 - Composition pour l'impression 3d - Google Patents

Composition pour l'impression 3d Download PDF

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Publication number
WO2018093230A2
WO2018093230A2 PCT/KR2017/013240 KR2017013240W WO2018093230A2 WO 2018093230 A2 WO2018093230 A2 WO 2018093230A2 KR 2017013240 W KR2017013240 W KR 2017013240W WO 2018093230 A2 WO2018093230 A2 WO 2018093230A2
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WIPO (PCT)
Prior art keywords
composition
magnetic
particles
printing
gas
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PCT/KR2017/013240
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English (en)
Korean (ko)
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WO2018093230A3 (fr
Inventor
박새봄
이진규
안상범
Original Assignee
주식회사 엘지화학
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Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201780057598.XA priority Critical patent/CN109715720B/zh
Priority to EP17871708.8A priority patent/EP3543287B1/fr
Priority to JP2019512628A priority patent/JP6943951B2/ja
Priority to US16/462,449 priority patent/US11232891B2/en
Publication of WO2018093230A2 publication Critical patent/WO2018093230A2/fr
Publication of WO2018093230A3 publication Critical patent/WO2018093230A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/23—Magnetisable or magnetic paints or lacquers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/20—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder
    • H01F1/28—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of particles, e.g. powder dispersed or suspended in a bonding agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/10—Formation of a green body
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2262—Oxides; Hydroxides of metals of manganese
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/01—Magnetic additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the present application relates to a composition for 3D printing, a 3D printing method using the same, and a three-dimensional shape including the same.
  • the present application relates to a magnetic composite that can be applied to three-dimensional printing and an ink composition comprising the same.
  • Three-dimensional printers have a three-dimensional printing mechanism configured to form physical objects three-dimensionally.
  • studies related to a composition for 3D printing continue.
  • the present application relates to a composition used as an ink of a 3D printer, and provides a composition capable of realizing precise formation of three-dimensional three-dimensional shapes and uniform curing properties of three-dimensional shapes.
  • the present application relates to a composition for 3D printing.
  • the 3D printing composition may be applied to, for example, printing a three-dimensional physical object to form a three-dimensional shape.
  • the composition may also be applied to sealing electronic devices.
  • the composition can be applied to encapsulating microelectronic devices, eg micro batteries.
  • Exemplary 3D printing compositions may include magnetic body particles and gas-containing particles.
  • the magnetic body particles and the gas-containing particles may form a magnetic body composite.
  • the magnetic body particles may surround the gas-containing particles, or the gas-containing particles may surround the magnetic body particles to form a magnetic body composite.
  • the composition for 3D printing includes the magnetic composite, as described below, the composition may be cured by vibrating heat of magnetic particles, and uniform curing may be performed by gas-containing particles.
  • the magnetic particles may have two or more magnetic domains (Multi-Magnetic Domains).
  • the magnetic particles may be magnetized by an external alternating magnetic field irregularly arranged in the absence of an external magnetic field.
  • the meaning that the magnetic domains are irregularly arranged in the above may mean that the magnetic directions present in the magnetic domains are different from each other and are not aligned, and in this case, the net value of the magnetization at room temperature may be zero and no magnetic properties.
  • the magnetic direction of the magnetic domains is aligned, whereby the magnetic particles can be magnetized.
  • the magnetic particles may be super-paramagnetic particles, but are not limited thereto.
  • the composition is three-dimensionally applied to form a three-dimensional shape, and generates vibration heat from the magnetic particles through the application of a magnetic field, thereby uniformly curing the entire composition for 3D printing.
  • the present application generates vibration heat by the magnetization reversal of the magnetic particles through the electromagnetic induction heating, it is possible to cure the thermosetting resin to be described later with the generated heat.
  • heat is generated by eddy current, which is generated by hysteresis loss of a metal or magnetic material.
  • the present application may generate heat due to vibration between magnetic bodies other than eddy current.
  • the magnetic body vibrates due to the coercive force of the magnetic particles under an external magnetic field, and the resin can be cured by using heat generated at this time, and the curing proceeds from the inside of the composition, thereby providing excellent physical properties.
  • the present application can implement a uniform and stable curing.
  • the magnetic particles may include two or more magnetic domains.
  • the term "magnetic domain” generally refers to a region in which magnetization directions are divided differently in a magnetic body.
  • magnetic particles having two or more magnetic domains are strongly magnetized by an external alternating magnetic field to generate vibration heat, and when the magnetic field is eliminated, the magnetic particles return to the original magnetic domain, thereby providing magnetic particles having low residual magnetization of hysteresis loss. have.
  • the material of the magnetic particles is not particularly limited.
  • the magnetic material may include pure iron, iron oxide, ferrite, iron alloy, cobalt alloy, nickel alloy or manganese alloy.
  • the magnetic particles may have a spherical shape, an ellipsoid, a tetrahedron, a hexahedron, a triangular pillar, a square pillar, a cylinder, an elliptic pillar, a polygonal pillar, or an amorphous shape.
  • the magnetic particles may be spherical.
  • the density of the magnetic particles may be appropriately selected in consideration of the purpose of the present application.
  • the density of the particles may be 1 g / cm 3 to 10 g / cm 3 , 1.5 g / cm 3 to 8.5 g / cm 3 or 3 g / cm 3 to 7 g / cm 3 .
  • the magnetic particles may be combined with the above-described gas-containing particles in the above density range, and may be dispersed in a uniform distribution during 3D printing to realize uniform curing.
  • the magnetic particles may have a coercive force in the range of 1 to 200 kOe, 10 to 150 kOe, 20 to 120 kOe, 30 to 100 kOe 40 to 95 kOe or 50 to 95 kOe.
  • the term "magnetism" may refer to the strength of the critical magnetic field required to reduce the magnetization of the magnetic material to zero. More specifically, the magnetic material magnetized by the external magnetic field maintains a certain degree of magnetization even after the magnetic field is removed, and the strength of the magnetic field that can cause the magnetization degree to be zero by applying a reverse magnetic field to the magnetized magnetic material is called coercive force. do.
  • the coercive force of the magnetic material may be a criterion for distinguishing the soft magnetic material or the hard magnetic material, and the magnetic particle of the present application may be the soft magnetic material.
  • the present application by controlling the coercive force of the magnetic particles in the above range, it is possible to easily implement the magnetic conversion of the magnetic body to generate the vibration heat of the degree desired in the present application to satisfy the desired degree of curing properties by the uniform curing of the resin have.
  • the measured temperature when the measured value is a value fluctuated by temperature with respect to the property value measured in the present application, the measured temperature may be room temperature, for example, 25 ° C.
  • the magnetic particles have a saturation magnetization value at 25 ° C. in the range of 20 to 150 emu / g, 30 to 130 emu / g, 40 to 100 emu / g, 50 to 90 emu / g or 60 to 85 emu / g.
  • the present application can control the saturation magnetization value of the magnetic particles relatively large, through which heat generated by vibration between magnetic particles, not eddy current, can satisfy the curing properties by uniform curing of the resin. Measurement of the physical properties of the magnetic particles in the present application may be calculated by the value of the Vibrating Sample Magnetometer (VSM).
  • VSM Vibrating Sample Magnetometer
  • VSM records the applied magnetic field by the Hall probe
  • the magnetization value of the sample is a device that measures the magnetization value of the sample by recording the electromotive force obtained when applying vibration to the sample by Faraday's law.
  • Faraday's law states that if the N pole of the bar magnet is pushed toward the coil, the galvanometer moves and the current flows through the coil. The resulting current is called induced current and is said to be generated by induced electromotive force.
  • VSM is a method of measuring the magnetization value of a sample by detecting the induced electromotive force in the search coil by applying the vibration to the sample by this basic operation principle.
  • the magnetic properties of the material can be measured simply as a function of magnetic field, temperature and time, allowing for a maximum magnetic force of up to 2 Tesla and a quick measurement in the temperature range of 2K to 1273K.
  • the average particle diameter of the magnetic particles may be in the range of 20nm to 300nm, 30nm to 250nm, 40nm to 230nm or 45nm to 220nm.
  • the average size of the magnetic domain of the magnetic particles may be in the range of 10 to 50nm or 20 to 30nm. The present application is within the particle size range, by controlling the number of magnetic domains and the size of the coercive force of the magnetic particles in an appropriate range, it is possible to generate heat to advance the uniform curing of the composition in the composition.
  • the present application can control the particle size to 20nm or more, thereby generating sufficient vibration heat during curing through low coercive force and a large number of magnetic domains, and by controlling below 300nm, the saturation magnetization value (saturation) while reducing the hysteresis loss of the magnetic body itself Only magnetization value) is present, thereby achieving a uniform and stable curing.
  • the material is not particularly limited.
  • the magnetic particles may satisfy the following formula (1).
  • M is a metal or metal oxide
  • X includes Fe, Mn, Co, Ni or Zn,
  • , c is a cationic charge of X and d is an anionic charge of oxygen.
  • M can be Fe, Mn, Mg, Ca, Zn, Cu, Co, Sr, Si, Ni, Ba, Cs, K, Ra, Rb, Be, Li, Y, B or oxides thereof have.
  • X a O b is Fe 2 O 3 c may be +3, d may be -2.
  • X a O b is Fe 3 O 4
  • c may be +2 and +3, and d may be -2.
  • Magnetic particles of the present application is not particularly limited as long as the above formula (1) is satisfied, for example, may be MFe 2 O 3 .
  • the 3D printing composition of the present application may include the magnetic particles may include the compound of Formula 1 alone, or may include a mixture of the compound of Formula 1 or a compound doped with an inorganic material to the compound of Formula 1.
  • the inorganic material may include monovalent to trivalent cation metals or oxides thereof, and two or more kinds of cation metals may be used.
  • the magnetic particles may include those surface-treated on the particle surface. That is, the composition of the present application may include particles surface-treated with a metal, metal oxide, organic material, or inorganic material on the surface of the magnetic body particles. The present application can prevent the magnetic particles from losing the coercive force of the magnetic body by oxidation in air through the surface treatment.
  • the surface treatment can increase the compatibility with the filler, dispersant organic solvent, and the like described later, can improve the dispersibility of the composition.
  • the surface treatment may form a polymer of polymethyl methacrylate (PMMA) on the surface by attaching a methyl methacrylate (MMA) monomer to the magnetic particles having a carboxyl group on the surface.
  • PMMA polymethyl methacrylate
  • MMA methyl methacrylate
  • the surface of the magnetic particles may be acid treated to remove the surface oxide film and surface treated, and surface treatment may also be performed by coating silica particles.
  • the gas containing particles may be hollow particles.
  • the gas-containing particles may have a structure in which one or more pores are included in the particles, and the gas is filled in the pores.
  • the gas-containing particles may include inorganic, organic or organic-inorganic composites.
  • the inorganic particles as the gas-containing particles may include one or more selected from the group consisting of silicate, silica, titanium, and iron, but is not limited thereto.
  • the organic particles as the gas-containing particles may include one or more selected from the group consisting of liposomes, polymers, and hydrogels, but are not limited thereto.
  • the gas-containing particles may mean a form in which a bubble is contained in a liquid or a solid, but is not limited thereto, and any form in which a hole is present in the particles may be included.
  • Materials containing such gases include glass (eg, Soda-lime-borosilicate glass), polymers, surfactants, lipids, proteins (eg albumin), silica, ceramics or metals (eg titanium oxides) , Carbon materials (eg, graphene) or combinations thereof.
  • the bubble may be a micro bubble or a nano bubble composed of the materials.
  • the gas of the gas-containing particles may include air, nitrogen, carbon dioxide, methane gas, perfluorocarbons, and the like.
  • the gas-containing particles may have a spherical shape, an ellipsoid, a tetrahedron, a hexahedron, a triangular pole, a square pole, a cylinder, an ellipse pole, a polygonal pole, or an amorphous shape.
  • the gas-containing particles may be spherical.
  • the density of the gas-containing particles may be appropriately selected in consideration of the purpose of the present application.
  • the density of the gas-containing particles may range from 0.01 g / cm 3 to 1.02 g / cm 3 , 0.1 g / cm 3 to 0.95 g / cm 3 or 0.2 g / cm 3 to 0.8 g / cm 3 .
  • the density in the present application can be used to infer the density by dispersing the particles in a solvent having a specific density.
  • the present application by adjusting the density of the gas-containing particles in the above range, it is possible to provide a composition having low density of the composite and long-term dispersion stability by being bonded to the above-described magnetic particles, and at the same time can implement excellent 3D printing performance .
  • the average size of the gas-containing particles may be appropriately selected in consideration of the purpose of the present application.
  • the average size of the gas-containing particles may be 10 nm to 100 ⁇ m, 50 nm to 90 ⁇ m, 100 nm to 50 ⁇ m, 200 nm to 30 ⁇ m, or 500 nm to 25 ⁇ m.
  • the average size of the composite may be appropriately selected in consideration of the purpose of the present application.
  • the average size of the complex may be 10 nm to 1000 ⁇ m, 50 nm to 900 ⁇ m, 100 nm to 500 ⁇ m, 200 nm to 300 ⁇ m or 500 nm to 250 ⁇ m.
  • the density of the composite may be appropriately selected in consideration of the purpose of the present application.
  • the complex has a density of 0.1 g / cm 3 to 10 g / cm 3 , 0.5 g / cm 3 to 8 g / cm 3 , 1.5 g / cm 3 to 7 g / cm 3 or 3.5 g / cm 3 to May be 5.5 g / cm 3 .
  • the density of the composite is within the above range it can ensure long-term dispersion stability in the composition, it can implement excellent 3D printing performance.
  • the magnetic particles and gas-containing particles may have their surfaces physically or chemically bonded to each other.
  • the magnetic particles and the gas-containing particles can be bonded through a particle-to-particle bonding method known in the art, the method is not particularly limited.
  • the magnetic particles and the gas-containing particles may have their surfaces bonded to each other by acid base reaction, electrostatic attraction, covalent bond, or hydrophilic to hydrophobic interaction.
  • an acid base reaction may be used, and specifically, the magnetic particles are surface treated with a substituent of any one of an acid group and a base, and the surface of the gas-containing particles is treated with another substituent, followed by an aqueous solution. It can be combined through the reaction.
  • the gas-containing particles may be included in 80 to 200 parts by weight, 90 to 180 parts by weight, 100 to 170 parts by weight or 110 to 160 parts by weight with respect to 100 parts by weight of the magnetic particles.
  • the present application is to have a uniform dispersibility in the ink composition in the above content range, it is possible to implement excellent 3D printing performance within the above range.
  • the 3D printing composition may further include a dispersant so that the magnetic particles may be uniformly dispersed.
  • a dispersant which can be used here, surfactant which has affinity with the surface of magnetic body particle
  • a dispersant a type containing an acid or a basic group, a high molecular weight acrylic polymer type having a weight average molecular weight of 10,000 or more, an inorganic soda type, and a metal salt type dispersant may be exemplified, and the composition of the present application may include at least one dispersant. It may include.
  • the dispersant may be included as 0.01 to 10 parts by weight, 0.1 to 8 parts by weight or 0.15 to 5 parts by weight with respect to 100 parts by weight of the thermosetting resin to be described later.
  • the composition for 3D printing may further include a dispersion medium.
  • a dispersion medium an inorganic solvent or an organic solvent can be used. Water etc. can be illustrated as said inorganic solvent.
  • the organic solvent may include hexane, ethanol, silicone oil or polydimethylsiloxane.
  • the content of the composite in the dispersion medium may be appropriately selected in consideration of the purpose of the present application or the application field of the composition.
  • the content of the composite in the dispersion medium is 0.1 wt% to 90 wt%, 0.5 to 80 wt%, 1 to 70 wt%, 3 to 55 wt%, 4 to 30 wt%, 4.5 to 15 wt% or 4.8 to 9 wt Can be%.
  • the density of the dispersion medium may be appropriately selected in consideration of the purpose of the present application.
  • the density of the dispersion medium may be, for example, 0.5 g / cm 3 to 2 g / cm 3 , 0.8 g / cm 3 to 1.8 g / cm 3 or 1.2 g / cm 3 to 1.5 g / cm 3. have. If the density of the dispersion medium is within the above range it may be more advantageous to ensure the dispersion stability of the composite.
  • the composition for 3D printing may form a magnetic cluster.
  • Magnetic particles of nanoparticle size form nanoclusters, thereby preventing agglomeration between magnetic bodies and improving dispersibility, thereby effectively curing the composition by vibrating heat.
  • the 3D printing composition of the present application may comprise a curable compound.
  • the curable compound may be a thermosetting resin.
  • thermosetting resin means a resin that can be cured through an appropriate heat application or aging process.
  • thermosetting resin in the present application is not particularly limited as long as it has the aforementioned characteristics.
  • the thermosetting resin may include at least one thermosetting functional group.
  • it may be cured to exhibit adhesive properties, and may include one or more thermosetting functional groups such as epoxy groups, glycidyl groups, isocyanate groups, hydroxy groups, carboxyl groups or amide groups.
  • specific types of the resin may include an acrylic resin, a polyester resin, an isocyanate resin, an ester resin, an imide resin, an epoxy resin, and the like, but is not limited thereto.
  • thermosetting resin aromatic or aliphatic; Or an epoxy resin of linear or branched chain type can be used.
  • an epoxy resin having an epoxy equivalent of 180 g / eq to 1,000 g / eq may be used as containing two or more functional groups.
  • an epoxy resin having an epoxy equivalent in the above range it is possible to effectively maintain properties such as adhesion performance and glass transition temperature of the cured product.
  • epoxy resins include cresol novolac epoxy resins, bisphenol A epoxy resins, bisphenol A novolac epoxy resins, phenol novolac epoxy resins, tetrafunctional epoxy resins, biphenyl epoxy resins, and triphenol methane types.
  • a kind or mixture of an epoxy resin, an alkyl modified triphenol methane epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, or a dicyclopentadiene modified phenol type epoxy resin is mentioned.
  • an epoxy resin preferably containing a cyclic structure in a molecular structure can be used, and more preferably an epoxy resin containing an aromatic group (for example, a phenyl group) can be used.
  • an epoxy resin containing an aromatic group for example, a phenyl group
  • the cured product may have excellent thermal and chemical stability.
  • aromatic group-containing epoxy resin examples include biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene modified phenol type epoxy resin, cresol type epoxy resin, Bisphenol-based epoxy resins, xylox-based epoxy resins, polyfunctional epoxy resins, phenol novolac epoxy resins, triphenol methane-type epoxy resins and alkyl-modified triphenol methane epoxy resins, such as one or a mixture of two or more, but is not limited thereto. no.
  • the composite may include 0.01 to 25 parts by weight, 0.1 to 20 parts by weight, 1 to 15 parts by weight, 3 to 13 parts by weight, or 5 to 12 parts by weight based on 100 parts by weight of the thermosetting resin.
  • a unit "weight part" means the weight ratio between each component.
  • the composition for 3D printing may further include a thermosetting agent.
  • the curing agent may further include a curing agent capable of reacting with the thermosetting resin to form a crosslinked structure or the like.
  • An appropriate kind can be selected and used according to the kind of functional group contained in the resin.
  • the curing agent may be a curing agent of an epoxy resin known in the art, for example, an amine curing agent, an imidazole curing agent, a phenol curing agent, a phosphorus curing agent, or an acid anhydride curing agent.
  • an epoxy resin known in the art, for example, an amine curing agent, an imidazole curing agent, a phenol curing agent, a phosphorus curing agent, or an acid anhydride curing agent.
  • One kind or more than one kind may be used, but is not limited thereto.
  • the curing agent may be an imidazole compound which is solid at room temperature and has a melting point or decomposition temperature of 80 ° C. or higher.
  • an imidazole compound which is solid at room temperature and has a melting point or decomposition temperature of 80 ° C. or higher.
  • the content of the curing agent may be selected according to the composition of the composition, for example, the type or ratio of the thermosetting resin.
  • the curing agent may be included in an amount of 1 part by weight to 20 parts by weight, 1 part by weight to 10 parts by weight, or 1 part by weight to 8 parts by weight, based on 100 parts by weight of the thermosetting resin.
  • the weight ratio may be changed depending on the type and ratio of the functional group of the thermosetting resin, or the crosslinking density to be implemented.
  • the 3D printing composition may further comprise a filler.
  • the filler may be an organic filler, an inorganic filler or a mixture thereof. Specific types of fillers that can be used in the present application are not particularly limited and include, for example, carbon black, carbon nanotubes, glass fibers, silica, synthetic rubber, TiO 2 , organic / inorganic pigments, clay, or talc. Or a mixture of two or more kinds may be used.
  • the filler may be included as 1 to 100 parts by weight, 10 to 80 parts by weight or 20 to 60 parts by weight relative to 100 parts by weight of the thermosetting resin.
  • the present application can secure mechanical properties (stiffness and reinforcement) after the composition is cured, and can improve the dispersibility and bonding property between the nano-sized magnetic material and the organic material.
  • the composition for 3D printing of the present application may include a thermoplastic resin.
  • the thermoplastic resin is, for example, acrylic resin, silicone resin, fluorine resin, styrene resin, polyolefin resin, thermoplastic elastomer, polyoxyalkylene resin, polyester resin, polyvinyl chloride resin, polycarbonate resin, polyphenylene sulfide resin , Polyurethane, cellulose resins, polyacetal resins or polyamide resins.
  • styrene resin for example, styrene-ethylene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), acrylonitrile-butadiene-styrene block copolymer (ABS) , Acrylonitrile-styrene-acrylate block copolymers (ASA), styrene-butadiene-styrene block copolymers (SBS), styrene-based homopolymers or mixtures thereof.
  • SEBS styrene-ethylene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • ABS acrylonitrile-butadiene-styrene block copolymer
  • ASA Acrylonitrile-styrene-acrylate block
  • the olefin resin for example, a high density polyethylene resin, a low density polyethylene resin, a polypropylene resin or a mixture thereof can be exemplified.
  • the thermoplastic elastomer for example, an ester thermoplastic elastomer, an olefin thermoplastic elastomer, a mixture thereof, or the like can be used.
  • polybutadiene resin or polyisobutylene resin may be used as the olefinic thermoplastic elastomer.
  • the polyoxyalkylene resins include polyoxymethylene resins, polyoxyethylene resins, mixtures thereof, and the like.
  • polyester resins examples include polyethylene terephthalate resins, polybutylene terephthalate resins, and mixtures thereof.
  • polyvinyl chloride resin polyvinylidene chloride etc. can be illustrated, for example.
  • a mixture of hydrocarbon resins may be included, for example, hexatriacotane or paraffin may be exemplified.
  • polyamide resin nylon etc. can be illustrated, for example.
  • acrylate resin polybutyl (meth) acrylate etc. can be illustrated, for example.
  • silicone resin polydimethylsiloxane etc. can be illustrated, for example.
  • polytrifluoroethylene resin polytetrafluoroethylene resin, polychlorotrifluoroethylene resin, polyhexafluoropropylene resin, polyvinylidene fluoride, polyvinylidene fluoride, polyfluoro Ethylene propylene propylene or mixtures thereof and the like can be exemplified.
  • the above-listed resins may be used, for example, by grafting with maleic anhydride, or the like, or may be used after being copolymerized with other listed resins or monomers for preparing the resins, or may be modified with other compounds.
  • the other compounds include carboxyl-terminated butadiene-acrylonitrile copolymers.
  • the composition for 3D printing according to the present application may include various additives depending on the use, the type of thermosetting resin, and the 3D printing process described later, in a range that does not affect the effects of the above-described invention.
  • the resin composition may include a coupling agent, a crosslinking agent, a curable material, a tackifier, an ultraviolet stabilizer, an antioxidant, or the like in an appropriate range of contents depending on the desired physical properties.
  • the curable material may mean a material having a thermosetting functional group and / or an active energy ray curable functional group which are separately included in addition to the components constituting the composition described above.
  • the present application also relates to a 3D printing method.
  • Exemplary 3D printing methods may include applying the above-described composition three-dimensionally to form a three-dimensional shape.
  • the composition is three-dimensionally applied to form a three-dimensional shape, and then generates vibration heat from the magnetic particles through a magnetic field applying step, thereby uniformly curing the composition.
  • the step of applying the magnetic field is not particularly limited and may be performed by a person skilled in the art by a known method.
  • the step of applying a magnetic field is a magnetic field for 20 seconds to 60 minutes, 30 seconds to 30 minutes or 30 seconds to 200 seconds at a current of 50A to 500A, 80A to 450A or 120A to 430A at a frequency of 100kHz to 1GHz Can give
  • applying the magnetic field may comprise at least two or more multiprofile schemes.
  • the multi-profile method may be performed at a frequency of 100 kHz to 1 GHz.
  • the multi-profile method is a first step of applying a magnetic field for 20 seconds to 10 minutes at a current of 10A to 80A, a second step of applying a magnetic field for 20 seconds to 10 minutes at a current of 80A to 130A and 150A to It may include a third step of applying a magnetic field for 5 seconds to 5 minutes at a current of 500A.
  • the step of applying the magnetic field may proceed in a manner that gives a gradient difference of the profile.
  • the method is applied by adjusting the intensity of the magnetic field in a stepwise manner, but giving the slope difference prevents rapid heat generation by increasing the magnetic field sequentially over time at 100 to 200 A.
  • thermal decomposition may occur to prevent deterioration of the properties of the cured product.
  • the thermal curing may proceed by applying a magnetic field as described above, and may include additional heat for 30 minutes to 24 hours at 40 °C to 100 °C after applying the magnetic field.
  • the present invention is not limited thereto, and heat may be applied together with application of a magnetic field.
  • the present application also relates to a three-dimensional solid shape.
  • the three-dimensional shape may include a cured product of the composition for 3D printing described above.
  • microelectronic devices can include cured products containing the aforementioned compositions.
  • the cured product may be applied as a sealing material, but is not limited thereto.
  • the microelectronic device may include a micro battery, a biosensor, or an actuator.
  • the present application can provide a display device using the composition described above as a sealing material.
  • the present application provides a composition that can realize the precise formation of three-dimensional solid shape and uniform curing properties of the three-dimensional shape.
  • Magnetic particles Fe 2 O 3 particles, Multi-Magnetic Domains, average particle diameter of about 100 nm: measured by Field Emission Scanning Electron Microscope (using DLS)
  • the acid-treated magnetic particles were dispersed in a polyacrylic acid aqueous solution and treated for 15 minutes with about 120 W of ultrasonic waves.
  • a magnetic body particle-glass bubble particle composite was prepared by reacting 0.3 g of glass bubble particles (average particle size about 18 ⁇ m) substituted with an amine group with the magnetic particles in the aqueous solution to surround magnetic particles on the surface of the glass bubble particles. do.
  • KSR-177 of Kukdo Chemical as an epoxy resin and an imidazole series curing agent of Shikoku C11ZA as a curing agent were mixed at a weight ratio of 90: 5 (KSR-177: C11ZA).
  • KSR-177: C11ZA an imidazole series curing agent of Shikoku C11ZA
  • the prepared composition was laminated on the support, and the magnetic field was applied for 180 seconds at a current value of 100 A in the external alternating magnetic field generating device.
  • Application of the magnetic field was applied to the magnetic field by adjusting the current value and time of the magnetic field generating device (Ambrell Easyheat) by putting the composition in a sample vial in a solenoid coil (3turns, OD 50mm, ID 35mm).
  • the resin composition was cured with vibration heat generated through the application of the magnetic field to form a pattern or three-dimensional shape.
  • a composition for 3D printing was prepared in the same manner as in Example 1, except that MnOFe 2 O 3 particles (Multi-Magnetic Domains, average particle diameter: about 100 nm: measured by Field Emission Scanning Electron Microscope (using DLS)) were used as magnetic particles. , A three-dimensional shape was formed.
  • MnOFe 2 O 3 particles Multi-Magnetic Domains, average particle diameter: about 100 nm: measured by Field Emission Scanning Electron Microscope (using DLS)
  • a magnetic body particles As a magnetic body particles, a ferromagnetic (Hard Type) Fe 2 O 3 particles (Single-Magnetic Domain, average particle diameter of about 100nm), a bisphenol-based epoxy resin and a curing agent were respectively mixed in a weight ratio of 5: 95: 5 to prepare a resin composition. .
  • a ferromagnetic (Hard Type) Fe 2 O 3 particles Single-Magnetic Domain, average particle diameter of about 100nm
  • a bisphenol-based epoxy resin and a curing agent were respectively mixed in a weight ratio of 5: 95: 5 to prepare a resin composition. .
  • the prepared composition was laminated on the support, and the magnetic field was applied for 180 seconds at a current value of 100 A in the external alternating magnetic field generating device.
  • Application of the magnetic field was applied to the magnetic field by adjusting the current value and time of the magnetic field generating device (Ambrell Easyheat) by putting the composition in a sample vial in a solenoid coil (3turns, OD 50mm, ID 35mm).
  • the resin composition was thermally cured with vibration heat generated through the application of the magnetic field, thereby forming a pattern or three-dimensional shape.
  • the magnetic particles dried at room temperature were put into a SQUID-Vibrating Sample Magnetometer (KISA), and the external magnetic field was measured by using an HS curve (VSM curve) at ⁇ 1 tesla. Measured.
  • thermocoupler was inserted immediately after application of a magnetic field, and the temperature inside a three-dimensional shape is confirmed.

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Abstract

La présente invention concerne une composition pour l'impression 3D, un procédé d'impression 3D faisant appel à celle-ci, et une forme tridimensionnelle comprenant la composition, et concerne une composition une composition d'encre qui peut former de façon précise une forme tridimensionnelle et présenter des propriétés de durcissement uniforme de la forme tridimensionnelle.
PCT/KR2017/013240 2016-11-21 2017-11-21 Composition pour l'impression 3d WO2018093230A2 (fr)

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CN201780057598.XA CN109715720B (zh) 2016-11-21 2017-11-21 用于三维打印的组合物
EP17871708.8A EP3543287B1 (fr) 2016-11-21 2017-11-21 Composition pour l'impression en 3 dimensions
JP2019512628A JP6943951B2 (ja) 2016-11-21 2017-11-21 ３ｄプリンティング用組成物
US16/462,449 US11232891B2 (en) 2016-11-21 2017-11-21 Composition for 3 dimensional printing

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KR1020160155255A KR102202909B1 (ko) 2016-11-21 2016-11-21 3d 프린팅용 조성물
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JP2021191639A (ja) 2021-12-16
CN109715720A (zh) 2019-05-03
KR102202909B1 (ko) 2021-01-14
EP3543287B1 (fr) 2020-12-30
JP2019536890A (ja) 2019-12-19
JP6943951B2 (ja) 2021-10-06
US20190318857A1 (en) 2019-10-17
US11232891B2 (en) 2022-01-25
EP3543287A4 (fr) 2020-03-04
EP3543287A2 (fr) 2019-09-25
CN109715720B (zh) 2021-05-25
WO2018093230A3 (fr) 2018-11-29
JP7262878B2 (ja) 2023-04-24

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